Polyethyleneoxy azo fugitive tints



United States Patent 3,154,534 TQLYETHYLENEOXY AZO FUGITIWE TENTS Donald J. Gale and Hans H. Kuhn, Spartanburg, S.C.,

assignors to Deer-ing Milliken Research Corporation,

3,154,534 Patented Oct. 27, 1964 With the exception of Compound II, where n is 1 when R is H(OCH CH R R n and M have the values given above.

The following preparations and examples are illustras t b 513., a corporation of Delaware 5 tive of the compounds of this invention and methods for No Drawing. Filed Jan. 30, 1962, Ser. No. 169,961 their preparation. Th 2 i' i i h b PREPARATION I is invention re a es 0 nove ue in s aving su n 1 t f f0 substantian an textile One mole (195 g.) of N,N-d1-(hydroxyethyl)-M-tolu1- y e 6 1 y I y 10 di e, (II;R =HOCH CH -,R =CH )inaflaskequipped The novel tints of this invention have the formula Wlth Stmer: mermometar and gas lnlet tube near F bottom and a gas outlet tube near the top of the flask, is HmOHCHm B heated to 140 C. under nitrogen. About 200 mg. of SO M sodium is added as catalyst. Ethylene oxide is bubbled 3 into the molten, vigorously stirred material at a rate such that a slight amount of gas escapes from the outlet tube. The ethylene oxide addition is continued, with cooling g M to maintain the temperature between about 140l60 C., I 3 until the reaction mass weighs 700 g. A 100 g. portion wh r n is an Integer belween about 15 a 1 of this mass is transferred to a new reaction flask with i 2 2)n" havlng l Value glven above, 70 mg. of sodium and ethylene oxide is added until the y a y arlkaryl or aralkly, 2 hydrogen, y aryl, transferred mass weighs 644 g., thus producing N,N-di(hyalkaryl, afalkyl Ys and M l droxyethylpolyethyleneoxy)-aniline containing a total In t above Compounds, When 1 15 2 2)n of about 100 ethyleneoxy groups (III; n is preferably between about and 100 and more 25 R 0C H preferably between about 35 and 75; aryl, alkyl, alkaryl, 2 2)n aralkyl and alkoxy preferably contain from one to twelve n-.=50, R =CH Thi compound lt t about 53 (3 carbon atoms, and preferably are hydrocarbon, e.g., phenyl, naphthyl, methyl, ethyl, propyl, tolyl, mesityl, PREPARATION H benzyl, phenethyl, etc., any substituents thereon being The procedure of Preparation I is followed substitutof a non-functional and non-reactive nature which will ing one mole (182 g.) of N,N-dihydroxyethyl-aniline as not interfere in the reactions described below for preparthe starting material. There is thus-produced N,N-di(hying such compounds. When R is other than roxyethylethylpoiyethyleneoxy)-aniline containing atotal H(OCH2CH2)D of about 100 ethyleneoxy groups (III; n is preferably twice the above values. R1=H(OCH2CH2)!1 These tints have a pure blue color which produces a :50, R =H) als melting t ab ut 53 0, rich green when blended with a yellow fugitive tint, they are adequately acid and base stable, and are very fugitive PREPARATION In with respect to all textile fibers, according to the stand- 40 About 1 mole (4,512 g.) of N,N-di(hydroxyethylards set forth by the industry for fugitive tints useful polyethyleneoxy)-aniline obtained according to the profor temporarily identifying fibers, yarns or fabrics. A tint cedure of Preparation I (III; R =H(OCI-I CH n='50, of any structure having these properties is extremely dif- R =H) is dissolved in a mixture of 4 liters of water and ficult to obtain and is rare even in the class of tints hav- 2.14 moles (206.6 g.) of 37.8% hydrochloric acid. The ing a polyethoxy group in the molecule. mixture is cooled to 05 C. and with stirring a solution The compounds of this invention are prepared by the of 1.07 moles (74 g.) of sodium nitrite in 250 ml. of following series of reactions. water is added over a 30 minute period, maintaining the HOCH OH I H OCH CH R2 2 Q UHF-CH2 2 G N N- R1 B1 II III llNaNOz 21101 R: R: H(OCH2C z)n I H OCH2CH2 I1 H01 N NH: N- NO R1 -2HC1 Rt V IV lNaNO: 2H01 (|)H 1TH:

R2 H(OCH2OHI)n I Q VII 803M N- NEN (I) NazCO B1 C1- mixture at the temperature and continuing the stirring for an additional 30 minutes when the addition is complete. There is thus-producted the p-nitroso derivative of the starting compound, which compound should immediately thereafter be reduced to the more stable p-amino derivative.

PREPARATION IV Following the procedure of Preparation III, N,N-di(hydroxyethylpolyethyleneoxy)-aniline, prepared according to the procedure of Preparation H, is converted to the corresponding p-nitroso compound (IV;

n=50, R =H) PREPARATION V To the cool solution obtained according to Preparation III, containing the N, N-di(hydroxyethylpolyethyleneoxy-p-nitroso-m-toluidine (IV;

n=50, R =CH is added 7 moles (676 g.) of 37.8% hydrochloric acid with stirring followed by 3.5 moles (225 g.) of zinc dust. One-half of the latter is added over a thirty minute period followed, fifteen minutes later, by the remaining half over an additional thirty minute period. Stirring is continued until the characteristic yellow compound of the nitroso compound disappears, keeping the temperature at all times below 20 C. The excess zinc is removed by filtration leaving a clear solution containing the hydrochloric acid salt of N,N-di(hydroxyethylpolyethyleneoxy) p tolylenediamine.

PREPARATION VI Following the procedure of Preparation V, N,N-di- (hydroxyethylpolyethyleneoxy) p nitroso aniline, prepared according to the procedure of Preparation IV, is converted to N,N-di(hydroxyethylpolyethyleneoxy)-pphenylenediamine (V; R =H(OCH CH 11:50, R2=H).

PREPARATION VII To the solution obtained according to the procedure of Preparation V containing the hydrochloric acid salt of N,N di(hydroxyethylpolyethyleneoxy) p tolylenediamine (V; R =H(OCH CH n=50, R =CH is added 193 grams of 37.8% hydrochloric acid and the mixture is cooled to C. With vigorous stirring and cooling to maintain the temperature below about C., a solution of 1.01 mole (70 g.) of sodium nitrite in 280 ml. of water is quickly added. After 30 minutes, the excess nitrous acid is destroyed with sulfamic acid to provide a negative starch-iodide test. The solution is then carefully brought to a pH of 4 with dilute aqueous sodium carbonate, to provide the diazonium salt of N,N-

di(hydroxyethylpolyethyleneoxy) p tolylenediamine (VI; R =H(OCH CH n=50, R =CH PREPARATION VIH Following the procedure of Preparation VII, N, N- di(hydroxyethylpolyethyleneoxy) p phenylenediamine, prepared according to the procedure of Preparation VI, is converted to the corresponding diazonium salt (VI; R =H(OCH CH n=50, R =H).

Following the procedure of Preparations I-VIII, other compounds represented by Formula II, e.g., N,N-di(hydroxyethyl)-substituted m-toluidine, m-anisidine, m-diphenylamine, m-benzylaniline, m-tolylaniline, m-phenethylaniline and N-hydroxyethyl-substituted N-methylaniline, N-ethylaniline, N-phenylaniline, N-benzylaniline, N-tolylaniline, N-phenethylaniline, N-methyl-m-toluidine, N-methyl-m-anisidine, N-methyl-m-benzylaniline, and N- rnethyl-m-phenyl-aniline, are converted to the corresponding diazonium salts, i.e., compounds represented by Formula VI containing a total of about 100 polyethyleneoxy groups.

Similarly, the N,N-di(hydroxyethylpolyethyleneoxy) and N-hydroxyethylpolyethyleneoxy diazonium compounds represented by Formula VI and containing a total of about 15, 30, 50, 75, 100, 250 or 500 ethyleneoxy groups, and otherwise corresponding to the above-named compounds are prepared from the corresponding N,N- di(hydroxyethyl)- and N-hydroxyethyl compounds represented by Formula II by varying the amount of ethylene oxide reacted with the N,N-di(hydroxyethyl) or N-hydroxyethyl compound in the reaction described in Preparations I and II.

Example One mole, calculated on the basis of pure material, of 2-amino-1-naphthol-3,5-disulfonic acid (Chicago Acid) is dissolved in 1 liter of water and the solution brought to neutrality with sodium carbonate. To this solution is then added 4.5 moles (477 g.) of sodium carbonate and 200 g. of ice. To this cold solution is slowly added with vigorous stirring the still cold solution of the diazonium salt of N,N-di(hydroxyethylpolyethyleneoxy)- p-tolylenediamine (VI; R =H(OCH CH n=50,

obtained according to the procedure of Preparation IV. The brilliant blue tint is formed almost immediately. After one hour the mixture is filtered and neutralized with hydrochloric acid to a pH of 7. The tint is isolated by evaporation of the water at about 60 C. under vacuum, dissolving'the tint in benzene, toluene or xylene, filtering salts which precipitate, and distilling the solvent. A melt of the purified tint is obtained which solidifies on cooling.

' Example II Following the procedure of Example I exactly, but substituting the diazonium salt of N,N-di(hydroxyethylpolyethyleneoxy)-p-phenylenediamine prepared according to the procedure of Preparation VIII, there is produced the corresponding Chicago Acid coupling reaction product (I; R =H(OCH CH n=50, R =H) which is a brilliant blue fugitive tint.

Following the procedure of Example I, each of the diazonium compounds named in the paragraph following Preparation VIII containing a total of 100 ethyleneoxy groups react with 2-amino-1-naphthol-3,5-disulfonic acid to produce the corresponding coupling reaction product, i.e., compounds represented by Formula I wherein in the first six of the above described compounds, R is n is about 50, and R is methyl, methoxy, phenyl, benzyl, tolyl, and phenethyl, respectively, and in the remaining compounds n is about 100, and R and R are methyl and H, ethyl and H, phenyl and H, benzyl and H, tolyl 5 and H, phenethyl and H, methyl and methyl, methyl and methoxy, methyl and benzyl, and methyl and phenyl, respectively.

Similarly, the N,N-di(hydroxyethylpolyethyleneoxy) and N-hydroxyethylpolyethyleneoxy compounds contain- 0 ing a total of about 15, 30, 50, 75, 100, 250 or 500 ethyleneoxy groups and otherwise corresponding to the above-named diazonium salts (VI) can be coupled with Z-amino-1-naphthol-3,5-disulfonic acids to produce other blue fugitive tints of this invention represented by Formula I.

5 What is claimed is: 1. A compound of the formula wherein n is about 50.

(1)3: ITIHQ 

1. A COMPOUND OF THE FORMULA 